Post on 26-Feb-2021
MOFs in Catalysis
« The Emperor's New Clothes » ?
D. Farrusseng
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1 – Acid Catalysis2 – Acid/Base3 – Encapsulation4 – Organometallics / Enantioselective Cat.5 – Photocatalysis6 – Polymerisation
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1 – Acid Catalysis
• BASF patent 2002
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poly(propylene carbonate).
Soga, K.; Imai, E.; Hattori, I. Polym. J. 1981, 13, 407.Inoue, S.; Tsuruta, T.; Furukawa, J. Makromol. Chem. 1962, 53, 215
US20020279940
- Zn/btc- MOF-5
? ! ? !
O + CO2
Zn(OH)2/glutaric acid
• First catalyst generations
Mw = 60.000-75.000 g/mol
- ZnEt2/pyrogallol > ZnEt2/H2O- ZnO/glutaric acid > Zn(OH)2/glutaric acid > Cr(OOCCH3)3
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0
20
40
60
80
100
Yiel
d
4 2 2 4
Catalytic results on “MOF-5”
100°C
t-BuCl
13 x 6 12 x 8 16 x 8 15 x 9
BEA MOR AlCl3MOF-5
U. Ravon, MicroMeso Mat., 2010
• Model reaction
• “MOF-5” prepared by fast pecipitation– SBET = 500-700 m2/g
• “pure” MOF-5 (Prof. S. Kaskel)– SBET = 2500 m2/g– much less active when kept under Ar and with dried chemicals
4,4'-ditBu-bipy 2,4'-ditBu-bipy 2-tBu-bipy 4-tBu-bipy
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Zn-OH in “MOF-5” ?
Air24hrs
Zn4O(bdc)3•2DEF Zn3(µ3-OH)(bdc)2•2DEF
1.0 0.5 0.0 -0.5 -1.0 -1.5 -2.0δ 1H / ppm
• MOF-5 transforms to MOF-69C*
• Quantification by solid 1H NMR– Zn(µOH) : dbc = 1:20-30
16 14 12 10 8 6 4 2 0 -2 -4
δ / ppm
Zn-OHHH
HH
• MOF-5 with Zn-OH defects– 3-5% of Zn(OH)– SBET = 500-700 m2/g >> MOF-69C IRMOF-1 prec
IRMOF-1 solv
*S. Hausdorf, J. Phys. Chem. A, 2008, 112, 7567
U. Ravon, New J. Chem, (2008), 32,937-940
3800 3700 3600 3500 3400 3300 3200
IRMOF-1(basf)des IRMOF-prec MOF-69C
λ / cm-1
MOF-69C
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Bronsted function
• MOF-69C (Zn) : Zn3(µ3-OH)2(bdc)2
• MIL-53 (Ga) : Ga(µ2-OH)(bdc)
• MIL-68 (In) : In(µ2-OH)(bdc)
1D Class with bridging OH
SiO
H
Al
D. Farrusseng, in “Handbook of heterogeneous Catalyst Design”, Wiley (Ed. U. Ozkan), 2009
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Alkylation on MIL-53(Ga)
biphenyl
0 1 2 3 40
20
40
60
80
100
HBEA IRMOF-1-prec MIL-53(Ga)
Conv
ersio
n
Time / hr
IRMOF 1 MIL 53(Al) MIL 53(G ) H BEA H MOR AlCl30
20
40
60
80
100
Yiel
d
4,4'-ditBu-bipy 2,4'-ditBu-bipy 2-tBu-bipy 4-tBu-bipy
MIL-53
MOF-5 Al BEAGa MOR AlCl3
Patent FR 08/01.089
• MIL-53(Ga)>>>MIL-53(Al)
• MIL-53(Ga) active at room temperature !
toluene
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Brønsted mechanism ?
-0.2 0.0 0.2 0.4 0.6 0.8-2.5
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
Toluene
Benzene
CN-benzene
Br-benzene
σ
Cl-benzene
H H
Cl
H H
• Effect of inductive groups on reactivity (Hammett constant σ)
• Charge of the transition state (ρ)– Protonation of the aromatics
Log(rate) =Cst + σ.ρ
MIL-53(Ga)
HY
Log
(r/r0
)
CH3
H H
<<
ρ> 0, acylation (basic)ρ=0, Fe-beta (redox)ρ<0, H-zeolite (acid)
B. Coq et al, Applied Cat. A, 100(1993) 69
²
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Brønsted acidity: Measurements
700 3650 3600 3550Wavenumber(cm-1)
3670
3684
0 2150 2100 37
2145
Wavenumber(cm-1)
2135
• Site probing by CO adsorption at 100K (Prof. S. Bordiga)
• Brønsted acidity: MIL-53(Ga) > MIL-53(Al)
• No evidence of Lewis centers
∆ν(OH)=90 cm-1
D. Farrusseng, ChemCatChem, 2010
MIL-53 (Ga)
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Ga-MIL-53 vs. zeolite
A. Vimont et al, . Phys. Chem. C, Vol. 111, No. 1, 2007
MILs
Not in the same range !
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2 – ACID BASE
ZIF-8
Triglyceride > pore aperture
? ! ? !
0
10
20
30
40
50
60
70
80
90
100
0 1 2 3 4 5 6
time (h)
Est
er p
ropo
rtio
n (%
) Methanol
Ethanol
ZIF-8
ZnAl 2O 3 ZIF-8
ZnAl2O3
0
10
20
30
40
50
60
70
80
90
100
0 1 2 3 4 5 6
time (h)
Est
er p
ropo
rtio
n (%
) Methanol
Ethanol
ZIF-8
ZnAl 2O 3 ZIF-8
ZnAl2O3
O
O
O
O
R
O
O
R
R
+ 3R'-OH
OH
OH
HOR'O
O
R+ 3
C. Chizallet, et al., JACS, 2010, 132, 12365
• Esterfip process (ZnAl2O3)
14
External surface models of ZIF-8
0 200 400 600 800 1000
T (K) (P = 1 bar)
Zn
C
NHO
0 200 400 600300 500
{Zn-Im3}
{Zn -Im2}
{Zn-Im}
T (K) (P = 10-6 bar)
100
A: in ambient air
B: in IR cell beforepre -treatment
C: in IR cell after activationD: in IR cell duringCO adsorption
E: catalysis
C. Chizallet, N. Bats, J. Phys. Chem. Lett, 2010, 1, 349
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Dissociation of MeOH on ZnIII and ZnII
Activation studies
Co- activation MeOH and Ester on ZnII
• Bulk can not activate MeOH• Actives centers : Zn-OH
• at external surfaces and/or structural defects
+1 0 kJ. mol- 1
C. Chizallet, et al., JACS, 2010, 132, 12365
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(g)
Acidité variéeA. . . CO
Nature of acid/base centers ?
• CO adsorption at 77K / DFT modelling
• Strong Zn(II) Lewis centers
• Strong Bronsted acid NH
• Weak basic sites OH and N-
• Activity at the surface
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alumina
SIM-1
alumina
SIM-1
Al
Zn
Enginnering: egg-shell catalyst
O OHSIM-1/γ-Al2O3 beads
iPrOH-iPrOK80°C, 10 h.
up to 90% yield after 2 runs
Aguado et al, Chem. Commun. 2010, 46, 7999-8001
SIM-1
Engineering : post-hydrophobisation
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3 - ENCAPSULATION
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MOFs: bridging pore size gap
LTAMFIFAU
AlPO4-5VPI-5
ITQ-33ITQ-37
MCM-41MOF-11
HKUST-1MIL-103
ZIF-8MOF-101
ZIF-70MOF-5JUC-48
MIL-100UMCM-1MIL-101
MIL-101-ndc
0 5 10 15 20 25 30 35 40 45 50Pore size / Å
egg albuminhemoglobinmyoglobininulinTIPB
MTBEMeOHH2O
CO2
Metal Nanoparticle (Au@ZIF)
• CVI of [AuCOCl] / 30wrt%loading
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D.Esken R. Fischer, RUB
ZIF-90
ZIF-8
•HPA templating in HKUST-1
Cu(NO3)2 + HPW + H3BTC
seconds
Bajpe et al. Chem. Eur. J. 2010L. H. Wee et al, Chem. Comm, 2010F. Kapteijn, J. Catal, 2009
Quenching at 77K
hours
PTA 25% wt MIL-101
Nafion
PTA 25% wt MIL-101
Nafion
EsterificationHPW@MIL-101
Heteropoly acids HPW/MOF
• Catalysis• Knoevenagel•MeOH deydration•Esterfication
Complexes in MOFs
• Encapsulation of metallo-phthalocyanines
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N
NN
N
N
N
N
N
F
F
F
F
M
FF
F
FF
F
F
FF F
F
F N
NN
N
N
N
N
NFe
Pore window1.6x1.5 nm
MPcF16,(sol):≈1.3x1.3 nm
FePc(t-Bu)4,(sol):>1.7x1.7 nm
OH
O
Tetralin
1-Tetralol
1-Tetralone
90°CAir
n(Tetralin):n(complex)=64000:1
Kockrick et al, Chem. Commun. 2010
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4 – Functional Ligands
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Sources of inspiration
Enzymes ZeolitesMOFs
• Organic
• Multinuclear sites
• Flexible
• Low thermal stability
• Inorganic
• Isolate acid sites
• Rigid
• High thermal stability
• Hybrid
• Multinuclear sites
• “Semi-rigid”
• 200-400°C
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8% ee !+ *
Kim et al. Nature, 404 (2000), 982
POST-1• Homochiral MOF• Lewis Base
? ! ? !
Esterification
• Enantioselectivity ?• Pore size effect ?
Asymmetric alcoholytic kinetic resolution of styrene oxide
27/38Tanaka, New Journal of Chemistry, 2010
28/38Hupp, Chem Comm, 2006Goldberg, Chem Comm, 2005
Bio-mimetic metallo-ligands
Mn(Salen)Porphyrin
PIZA-1
• Linker = bio-mimetic catalyst
Net interpenetration to adjust pore size
W. Lin, Nat. Chem, 2010
Characterisation…. Activity rate vs. Cost ?
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MOF-NH2 library for post-functionlisation
NH2
MIL-101 (Fe)4
NH2N
N
NH2NH2
NH2
NH2
MIL-53(Al3, Fe4)DMOF-12
UMCM-12
MIL-68 (In)5IRMOF-31
CAU-18
NH2
MOF-LIC-16
UiO-667
1 Eddaoudi, M. et al, Science, 2002, 295, 469-472. 5 Savonnet, M. et al, 2009, FR Patent 09/05.101. 2 Wang, Z. et al, Inorg. Chem. 2009, 48, 296-306. 6 Gamez, P. et al, Eur. J. Inorg. Chem., 2008, 1551-1554.3 Ahnfeldt, T. Inorg. Chem., 2009, 48, 3057-3064. 7 Cavka, J. H. et al, J. Am. Chem. Soc., 2008, 130, 13850 –13851.4 Bauer, S. et al, Inorg. Chem., 2008, 47, 7568. 8 Ahnfeldt, D. et al, Angew. Chem.-Int. Edit. 2009, 48, 5163-5166.
COOH
COOH
NH2
NH2
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Post-functionalisation methods
1 Wang, Z. Q et al, Chem. Soc. Rev. 2009, 38, 1315-1329. 5Ahnfeldt, T. Inorg. Chem., 2009, 48, 3057-3064.2 Dugan, E. et al, Chem. Commun., 2008, 3366-3368. Gamez, P. et al, Eur. J. Inorg. Chem., 2008, 1551-1554. 3 Ingleson, M. J.et al, Chem. Commun., 2008, 1287-1289. 6 Savonnet, M et al, Green Chem. 2009, 11, 1729-1732.Gamez, P. et al, Eur. J. Inorg. Chem., 2008, 1551-1554. 7 Christophe V.et al, Angew. Chem. Int. Ed., 2010, 49, 4644-4648.
4 Britt, D. et al, Inorg. Chem., 2010, 49, 6387-6389.
MOF-NH2
NH2
NH
R OO
RO
R
R NCONH
R HO
NR
R OHO
NHR
Cl RO
SClCl
O
ONH
R
O
NHR
O
NCS1
2
3 45
6
7
NH
H2N
HN
Post-functionalisation vs. Porosity ?
• One pot Click Chemistry
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N3 N
NN
MOF-N3 MOF-fun
NH2
MOF-NH2
TMSN3
0 20 40 60 80 1000
200
400
600
800
1000
1200
1400
BET
surfa
ce a
rea
(cm
².g-1
)
Degree of modification (%)
NH2
MIL-68(In)-NH2
NH2
CAU-12 3
NH2
MIL-68(In)-NH2
NH2
CAU-12 3
MIL-68
CAU-1
33/38Rosseinsky, Chem.Com, 2008
tBuOOHTHF/65°C72h
40% conversion
Surface Organometallic species
S. Cohen, Chem. Soc. Rev., 2009
NH2
O
N
HO
N
OV
O
O
Ac2O OCN-R
V(O)acac2
OHO
Lack of short range characterisation….
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5 – PhotoCatalysis
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MOFs: Photocatalysis
Gascon et al., ChemSusChem, 2008
Effect of the linker on the bandgap
S. Bordiga et al, Chem.Commun. 2004
Zn4O13 node = Quantum dotsLinkers = antenna for hv
• MOF-5 : photoluminescent material
ZnO
ex em
• MOF-5 : Strong oxidizing semi-conductor
Corma et al., J. Mater. Chem , 2010
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Polymerisation
• Topotactic polymerization in 1D MOF
Kitagawa et al, Angew. Chem., 2004
7.8 x 7.8 Mw/Mn=1.6
• Anionic polymerization of acetylene in 1D MOF
• Polycarbonates from epoxides & CO2 in 3D MOF(Zn)
Kitagawa et al, Nature, 2005
Mueller, US patent, 2003 Zinc glutarate = 2nd catalyst generation
Mw = 60.000-75.000 g/mol
Marketing ?
Enzymes ZeolitesMOFs
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Think different !
OH+
Metal0-SO3H
-NH2
hυ
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Flexibility & molecular recognition
• Pore flexibility upon guest adsorption
• Rotating ligand with Temperature
MIL-53
[Zn2(1,4-ndc)2-(dabco)]n
CPL-2
S. Kitagawa et al, Angew. Chem. 2006, 118, 5054
Towards biomimetism
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Thanks
Dr. Sonia AguadoDr. J. CanivetDr. C. GaudillereDr. U. RavonM. SavonnetC-H. NicolasT. LescouetDr. J. PawlesaDr. E. KockrickDr. J. SubletA. CamarataM. Bahssa
Dr. N. Bats, IFPENDr. C. Nieto, IFPENDr. G. Pirngruber, IFPENDr. F. Figueras, IRCELYONDr. C. Pinel, IRCELYONDr. A. Lesage, ENS-LyonDr. M. Baias, ENS-LyonDr. L. Emsley, ENS-Lyon
Prof. S. Kaskel, TUD